Fibrillated polymer compositions and methods of their manufacture

ABSTRACT

The disclosure is directed to polymer compositions comprising a matrix polymer component comprising a crystalline or semi-crystalline polymer; and a fibrillated fluoropolymer, a fibrillated fluoropolymer encapsulated by an encapsulating polymer, or a combination thereof. Methods of preparing and using these polymer compositions, as well as articles comprising the polymer compositions, as also described.

CROSS REFERENCE TO RELATED APPLICATION

The present application claims priority to U.S. application Ser. No.62/133,520, filed Mar. 16, 2015, the entirety of which is incorporatedherein by reference.

BACKGROUND

Many polymer-based articles are manufactured by injection, additivemanufacturing, biaxial drawing, pipe extrusion, and other moldingprocesses. In order to obtain good mechanical properties, differentapproaches have been attempted, such as use of fillers to reinforce thepolymers. Despite advances in the art and the success of many filledpolymer compositions, there remains a continuing need for improvedcombinations of properties such as higher modulus, improved ductility,improved impact, and/or improved melt flow characteristics, so thatmolding operations can be performed more rapidly and with improvedeconomics. Typically, it is difficult to obtain good complex viscosity,extensional viscosity, tensile modulus, and impact strength in aparticular polymer composition.

Polytetrafluoroethylene (PTFE) fibers have been used as fillers inpolymer compositions, but can aggregate in the matrix resin, making itvery difficult to obtain a uniform composition. Polytetrafluoroethyleneand other fluoropolymers have also been used as additives inthermoplastic polymers in order to improve certain properties of thepolymers. The use of relatively small amounts, for example about 0.1 toabout 1 percent by weight, of fluoropolymers as an anti-drip additive inflame retardant grades of thermoplastic resin molding compositions isdescribed, for example, in U.S. Pat. Nos. 4,810,739, 4,579,906, and4,810,739. The use of sintered PTFE in highly filled thermoplasticcompositions as low friction additives is disclosed in U.S. Pat. No.5,879,791. A drawback to the use of fluoropolymer additives exists,however, in that such additives have poor dispersibility in manypolymers.

Therefore, there is a continuing in the art for compositions, methods,and articles that can provide balanced mechanical and rheologicalproperty profiles.

SUMMARY

The above-described and other deficiencies of the art are met by polymercompositions comprising a matrix polymer component comprising acrystalline or semi-crystalline polymer; and 0.1 weight percent (wt. %)to 15 wt. %, or about 0.1 wt. % to about 15wt. %, based on the weight ofthe polymer composition, of a fibrillated fluoropolymer, a fibrillatedfluoropolymer encapsulated by an encapsulating polymer, or a combinationthereof.

In another embodiment are articles of manufacture comprising thesepolymer compositions. In still another embodiment of methods ofprocessing these polymer compositions.

The above described and other features are exemplified by the followingdrawings, detailed description, examples, and claims.

BRIEF DESCRIPTION OF THE DRAWINGS

The following is a brief description of the drawings wherein likeelements are numbered alike and which are exemplary of the variousembodiments described herein.

FIG. 1 depicts complex viscosity for embodiments of the disclosureincorporating PBT.

FIG. 2 depicts complex viscosity for embodiments of the disclosureincorporating PET with 1 wt. % PTFE.

FIG. 3 depicts extensional viscosity for embodiments of the disclosureincorporating PBT.

FIG. 4 depicts extensional viscosity for embodiments of the disclosureincorporating PET with 1% PTFE.

FIG. 5 depicts extensional viscosity for embodiments of the disclosureincorporating PP (random).

FIG. 6 depicts extensional viscosity for embodiments of the disclosureincorporating PP (copolymer).

FIG. 7 depicts extensional viscosity for embodiments of the disclosureincorporating PP (homopolymer).

FIG. 8 depicts tensile modulus for embodiments of the disclosureincorporating PBT.

FIG. 9 depicts notched impact strength for embodiments of the disclosureincorporating PBT.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

The present disclosure may be understood more readily by reference tothe following detailed description of desired embodiments and theexamples included therein. In the following specification and the claimsthat follow, reference will be made to a number of terms which have thefollowing meanings.

The present disclosure is directed to polymer compositions comprising amatrix polymer component comprising a crystalline or semi-crystallinepolymer; and a fibrillated fluoropolymer, a fibrillated fluoropolymerencapsulated by an encapsulating polymer, or a combination thereof.Methods of using these polymer compositions, as well as articles formedfrom these compositions, are also described. The described polymercompositions exhibit surprising melt strengths, making them suitable foruse in foaming, sheet, and pipe extrusion processes.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art. In case of conflict, the present document, includingdefinitions, will control. Preferred methods and materials are describedbelow, although methods and materials similar or equivalent to thosedescribed herein can be used in practice or testing of the presentdisclosure. All publications, patent applications, patents and otherreferences mentioned herein are incorporated by reference in theirentirety. The materials, methods, and examples disclosed herein areillustrative only and not intended to be limiting.

The singular forms “a,” “an,” and “the” include plural referents unlessthe context clearly dictates otherwise.

As used in the specification and in the claims, the term “comprising”may include the embodiments “consisting of” and “consisting essentiallyof”. The terms “comprise(s),” “include(s),” “having,” “has,” “can,”“contain(s),” and variants thereof, as used herein, are intended to beopen-ended transitional phrases, terms, or words that require thepresence of the named ingredients/steps and permit the presence of otheringredients/steps. However, such description should be construed as alsodescribing compositions or processes as “consisting of” and “consistingessentially of” the enumerated ingredients/steps, which allows thepresence of only the named ingredients/steps, along with any impuritiesthat might result therefrom, and excludes other ingredients/steps.

Numerical values in the specification and claims of this application,particularly as they relate to polymers or polymer compositions, reflectaverage values for a composition that may contain individual polymers ofdifferent characteristics. Furthermore, unless indicated to thecontrary, the numerical values should be understood to include numericalvalues which are the same when reduced to the same number of significantfigures and numerical values which differ from the stated value by lessthan the experimental error of conventional measurement technique of thetype described in the present application to determine the value.

All ranges disclosed herein are inclusive of the recited endpoint andindependently combinable (for example, the range of “from 2 grams to 10grams” is inclusive of the endpoints, 2 grams and 10 grams, and all theintermediate values). The endpoints of the ranges and any valuesdisclosed herein are not limited to the precise range or value; they aresufficiently imprecise to include values approximating these rangesand/or values.

As used herein, approximating language may be applied to modify anyquantitative representation that may vary without resulting in a changein the basic function to which it is related. Accordingly, a valuemodified by a term or terms, such as “about” and “substantially,” maynot be limited to the precise value specified, in some cases. In atleast some instances, the approximating language may correspond to theprecision of an instrument for measuring the value. The modifier “about”should also be considered as disclosing the range defined by theabsolute values of the two endpoints. For example, the expression “fromabout 2 to about 4” also discloses the range “from 2 to 4.” The term“about” may refer to plus or minus 10% of the indicated number. Forexample, “about 10%” may indicate a range of 9% to 11%, and “about 1”may mean from 0.9-1.1. Other meanings of “about” may be apparent fromthe context, such as rounding off, so, for example “about 1” may alsomean from 0.5 to 1.4.

The present disclosure is directed to polymer compositions comprising amatrix polymer component comprising a crystalline or semi-crystallinepolymer; and a fibrillated fluoropolymer, a fibrillated fluoropolymerencapsulated by an encapsulating polymer, or a combination thereof. Inpreferred embodiments, the polymer compositions comprise 0.1 wt. % to 15wt. %, or from about 0.1 wt. % to about 15 wt. %, based on the weight ofthe polymer composition, of a fibrillated fluoropolymer, a fibrillatedfluoropolymer encapsulated by an encapsulating polymer, or a combinationthereof. Methods of using these polymer compositions, as well asarticles formed from these compositions, are also described.

The polymer compositions of the description have mechanical andrheological properties that are surprising and unexpected. For example,the described polymer compositions have a complex viscosity, measured ata 0.1 rad/sec, of greater than 4500 Pa·s (Pascal-second), or greaterthan about 4500 Pa·s, preferably between about 4500 Pa·s and about70,000 Pa·s, for example, between 4500 Pa·s and 70,000 Pa·s. Forexample, the described polymer compositions have a complex viscosity ofabout 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500,10,000, 11,000, 12,000, 13,000, 14,000, 15,000, 16,000, 17,000, 18,000,19,000, 20,000, 25,000, 30,000, 35,000, 40,000, 45,000, 50,000, 55,000,60,000, 65,000, or about 70,000 Pa·s.

In other embodiments, the described polymer compositions have anextensional viscosity of greater than 11,000, preferably between about11,000 and about 90,000 Pa·s at a maximum henky strain of 2.0 at astrain rate of 15-1. For example, the described polymer compositionshave an extensional viscosity of about 11,000, 12,000, 13,000, 14,000,15,000, 16,000, 17,000, 18,000, 19,000, 20,000, 25,000, 30,000, 35,000,40,000, 45,000, 50,000, 55,000, 60,000, 65,000, 70,000, 75,000, 80,000,85,000, or about 90,000 Pa·s at a maximum henky strain of 2.0 at astrain rate of 1 s⁻¹. In still other embodiments, the described polymercompositions have a tensile modulus of greater than 2450 megapascals(MPa), preferably greater than 2450 to about 3000 MPa. For example, thedescribed polymer compositions have a tensile modulus of 2455, 2460,2465, 2470, 2475, 2480, 2485, 2490, 2495, 2500, 2510, 2520, 2530, 2540,2550, 2560, 2570, 2580, 2590, 2600, 2610, 2620, 2630, 2640, 2650, 2660,2670, 2680, 2690, 2700, 2710, 2720, 2730, 2740, 2750, 2760, 2770, 2780,2790, 2800, 2810, 2820, 2830, 2840, 2850, 2860, 2870, 2880, 2890, 2900,2510, 2920, 2930, 2940, 2950, 2960, 2970, 2980, 2990, or about 3000 MPa.In yet other embodiments, the described polymer compositions have anotched impact strength (ISO 180 at 23° C.) of greater than 3.5kilojoule per square meter (KJ/m²), or greater than about 3.5 KJ/m²,preferably 3.5 KJ/m² to about 10 KJ/m². For example, the describedpolymer compositions have a notched impact strength of 3.6, 3.7, 3.8,3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5, 5.1, 5.2, 5.3,5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8,6.9, 7, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8, 8.1, 8.2, 8.3,8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8,9.9, or about 10 KJ/m².

The matrix polymer component comprises one or more polymers that are notfibrillated during the mixing process described herein. Examples ofsuitable matrix polymers of the disclosure exclude polycarbonatepolymers. Suitable polymers are crystalline and semi-crystallinethermoplastic materials. Examples of suitable polymers are poly(ethyleneterephthalate) (PET), poly(1,4-butylene terephthalate) (PBT),poly(ethylene naphthanoate) (PEN), poly(butylene naphthanoate), (PBN),(polypropylene terephthalate) (PPT), polycyclohexanedimethanolterephthalate (PCT), polypropylene (PP) (including random, co-polymer,and homopolymer polypropylene), and combinations comprising at least oneof the foregoing polyesters. Also contemplated are the above polyesterswith a minor amount, e.g., from 0.5 to 10 percent by weight, or fromabout 0.5 to about 10 percent by weight, of units derived from analiphatic diacid and/or an aliphatic polyol to make copolyesters. Otheruseful polymers include nylon, linear low-density polyethylene (LLDPE),low-density polyethylene (LDPE), high density polyethylene (HDPE), andcombinations thereof Particularly preferred polymers for use in thematrix polymer are PBT, PET, and PP. The matrix polymer may generally beprovided in any form, including but not limited to powders, plates,pellets, flakes, chips, whiskers, and the like.

The polymer compositions described herein comprise 0.1 wt. % to 15 wt.%, or from about 0.1 wt. % to about 15 wt. %, based on the weight of thepolymer composition, of a fibrillated fluoropolymer, a fibrillatedfluoropolymer encapsulated by an encapsulating polymer, or a combinationthereof. According to the disclosure, the polymer compositions comprise0.1 wt. % to 15 wt. %, or from about 0.1 wt. % to about 15 wt. %, forexample, 1 wt. % to 10 wt. %, or from about 1 wt. % to about 10 wt. %,based on the weight of the polymer composition, of the fibrillatedfluoropolymer, the fibrillated fluoropolymer encapsulated by anencapsulating polymer, or the combination thereof. In some embodiments,the polymer compositions comprise about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6,0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5,8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, orabout 15 wt. %, based on the weight of the polymer composition, of thefibrillated fluoropolymer, the fibrillated fluoropolymer encapsulated byan encapsulating polymer, or the combination thereof.

Fluoropolymers suitable for use as the fluoropolymer component describedin U.S. Pat. No. 7,557,154 and are capable of being fibrillated(“fibrillatable”) during mixing with the matrix polymer, the filler, orboth simultaneously. “Fibrillation” is a term of art that refers to thetreatment of fluoropolymers so as to produce, for example, a “node andfibril,” network, or cage-like structure. Suitable fluoropolymersinclude but are not limited to homopolymers and copolymers that comprisestructural units derived from one or more fluorinated alpha-olefinmonomers, that is, an alpha-olefin monomer that includes at least onefluorine atom in place of a hydrogen atom. In one embodiment thefluoropolymer comprises structural units derived from two or morefluorinated alpha-olefin, for example tetrafluoroethylene,hexafluoroethylene, and the like. In another embodiment, thefluoropolymer comprises structural units derived from one or morefluorinated alpha-olefin monomers and one or more non-fluorinatedmonoethylenically unsaturated monomers that are copolymerizable with thefluorinated monomers, for example alpha-monoethylenically unsaturatedcopolymerizable monomers such as ethylene, propylene, butene, acrylatemonomers (e.g., methyl methacrylate and butyl acrylate), vinyl ethers,(e.g., cyclohexyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether,vinyl esters) and the like. Specific examples of fluoropolymers includepolytetrafluoroethylene, polyhexafluoropropylene, polyvinylidenefluoride, polychlorotrifluoroethylene, ethylene tetrafluoroethylene,fluorinated ethylene-propylene, polyvinyl fluoride, and ethylenechlorotrifluoroethylene. Combinations comprising at least one of theforegoing fluoropolymers may also be used. Polytetrafluoroethylene isparticularly preferred.

As is known, fluoropolymers are available in a variety of forms,including powders, emulsions, dispersions, agglomerations, and the like.“Dispersion” (also called “emulsion”) fluoropolymers are generallymanufactured by dispersion or emulsion, and generally comprise about 25to 60 weight % fluoropolymer in water, stabilized with a surfactant,wherein the fluoropolymer particles are approximately 0.1 to 0.3micrometers in diameter. “Fine powder” (or “coagulated dispersion”)fluoropolymers may be made by coagulation and drying ofdispersion-manufactured fluoropolymers. Fine powder fluoropolymers aregenerally manufactured to have a particle size of approximately 400 to500 microns. “Granular” fluoropolymers may be made by a suspensionmethod, and are generally manufactured in two different particle sizeranges, including a median particle size of approximately 30 to 40micrometers, and a high bulk density product exhibiting a medianparticle size of about 400 to 500 micrometers. Pellets of fluoropolymermay also be obtained and cryogenically ground to exhibit the desiredparticle size.

In one embodiment the fluoropolymer is at least partially encapsulatedby an encapsulating polymer that may be the same or different as thematrix polymer (hereinafter referred to as an “encapsulated polymer”).Without being bound by theory, it is believed that encapsulation may aidin the distribution of the fluoropolymer within the matrix, and/orcompatibilize the fluoropolymer with the matrix.

Suitable encapsulating polymers accordingly include, but are not limitedto, vinyl polymers, acrylic polymers, polyacrylonitrile, polystyrenes,polyolefins, polyesters, polyurethanes, polyamides, polysulfones,polyimides, polyetherimides, polyphenylene ethers, polyphenylenesulfides, polyether ketones, polyether ether ketones, ABS resins,polyethersulfones, poly(alkenylaromatic) polymers, polybutadiene, liquidcrystalline polymers, polyacetals, polycarbonates, polyphenylene ethers,ethylene-vinyl acetate copolymers, polyvinyl acetate, liquid crystalpolymers, ethylene-tetrafluoroethylene copolymer, aromatic polyesters,polyvinyl fluoride, polyvinylidene fluoride, polyvinylidene chloride,and combinations comprising at least one of the foregoing polymers.

Particularly preferred encapsulating polymers comprise astyrene-acrylonitrile copolymer, an acrylonitrile-butadiene-styrenecopolymer, alpha-alkyl-styrene-acrylonitrile copolymer, analpha-methylstyrene-acrylonitrile copolymer, a styrene-butadiene rubber,or a combination thereof. Styrene-acrylonitrile copolymer encapsulatedpolytetrafluoroethylene is one preferred embodiment.

The encapsulating polymers may be obtained by polymerization of monomersor mixtures of monomers by methods known in the art, for example,condensation, addition polymerization, and the like. Emulsionpolymerization, particularly radical polymerization may be usedeffectively. In one embodiment, the encapsulating polymer is formed frommonovinylaromatic monomers containing condensed aromatic ringstructures, such as vinyl naphthalene, vinyl anthracene and the like,.Examples of suitable monovinylaromatic monomers include styrene,3-methylstyrene, 3,5-diethylstyrene, 4-n-propylstyrene,alpha-methylstyrene, alpha-methyl vinyltoluene, alpha-chlorostyrene,alpha-bromostyrene, dichlorostyrene, dibromostyrene,tetra-chlorostyrene, and the like, and combinations comprising at leastone of the foregoing compounds. Styrene and/or alpha-methylstyrene maybe specifically mentioned.

Other useful monomers for the formation of the encapsulating polymerinclude monovinylic monomers such as itaconic acid, acrylamide,N-substituted acrylamide or methacrylamide, maleic anhydride, maleimide,N-alkyl-, aryl-, or haloaryl-substituted maleimide, and glycidyl(meth)acrylates. Other examples include acrylonitrile, ethacrylonitrile,methacrylonitrile, alpha-chloroacrylonitrile, beta-chloroacrylonitrile,alpha-bromoacrylonitrile, acrylic acid, methyl (meth)acrylate, ethyl(meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, n-propyl(meth)acrylate, isopropyl (meth)acrylate, 2-ethylhexyl (meth)acrylate,and the like, and combinations comprising at least one of the foregoingmonomers.

Mixtures of the foregoing monovinylaromatic monomers and monovinylicmonomers may also be used, for example mixtures of styrene andacrylonitrile (SAN). The relative ratio of monovinylaromatic andmonovinylic monomers in the rigid graft phase may vary widely dependingon the type of fluoropolymer, type of monovinylaromatic and monovinylicmonomer(s), and the desired properties of the encapsulant. Theencapsulant may generally be formed from up to 100 wt. %, or up to about100 wt. %, of monovinyl aromatic monomer, specifically 30 to 100 wt. %,or about 30 to about 100 wt. %, more specifically, 50 to 90 wt. %, orabout 50 to about 90 wt. % monovinylaromatic monomer, with the balancebeing comonomer(s). A preferred fluoropolymer is TSAN, which comprisesSAN and PTFE. See, U.S. Pat. Nos. 5,804,654 and 6,040,370.

Elastomers may also be used as the encapsulating polymer, as well aselastomer-modified graft copolymers. Suitable elastomers include, forexample, conjugated diene rubbers; copolymers of a conjugated diene withless than about 50 wt. % of a copolymerizable monomer; olefin rubberssuch as ethylene propylene copolymers (EPR) or ethylene-propylene-dienemonomer rubbers (EPDM); ethylene-vinyl acetate rubbers; siliconerubbers; elastomeric C1-8 alkyl (meth)acrylates; elastomeric copolymersof C1-8 alkyl (meth)acrylates with butadiene and/or styrene; orcombinations comprising at least one of the foregoing elastomers.

Examples of conjugated diene monomers that may be used are butadiene,isoprene, 1,3-heptadiene, methyl-1,3-pentadiene,2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-pentadiene; 1,3- and2,4-hexadienes, and the like, as well as mixtures comprising at leastone of the foregoing conjugated diene monomers. Specific conjugateddiene homopolymers include polybutadiene and polyisoprene.

Copolymers of a conjugated diene rubbers may also be used, for examplethose produced by aqueous radical emulsion polymerization of aconjugated diene and up to 10 wt. %, or up to about 10 wt. %, of one ormore monomers copolymerizable therewith. Specific copolymers includestyrene and acrylonitrile.

(Meth)acrylate monomers suitable for use as an elastomeric encapsulatingmonomer include the cross-linked, particulate emulsion homopolymers orcopolymers of C4-8 alkyl (meth)acrylates, in particular C4-6 alkylacrylates, for example n-butyl acrylate, t-butyl acrylate, n-propylacrylate, isopropyl acrylate, 2-ethylhexyl acrylate, and the like, andcombinations comprising at least one of the foregoing monomers.Exemplary comonomers include but are not limited to butadiene, isoprene,styrene, methyl methacrylate, phenyl methacrylate,phenethylmethacrylate, N-cyclohexylacrylamide, vinyl methyl ether oracrylonitrile, and mixtures comprising at least one of the foregoingcomonomomers. Optionally, up to 5 wt. % a polyfunctional crosslinkingcomonomer may be present, for example divinylbenzene, alkylenedioldi(meth)acrylates such as glycol bisacrylate, alkylenetrioltri(meth)acrylates, polyester di(meth)acrylates, bisacrylamides,triallyl cyanurate, triallyl isocyanurate, allyl (meth)acrylate, diallylmaleate, diallyl fumarate, diallyl adipate, triallyl esters of citricacid, triallyl esters of phosphoric acid, and the like, as well ascombinations comprising at least one of the foregoing crosslinkingagents.

Suitable elastomer-modified graft copolymers may be prepared by firstproviding an elastomeric polymer (for example, as described above), thenpolymerizing the constituent monomer(s) of the rigid phase in thepresence of the fluoropolymer and the elastomer to obtain the graftcopolymer. The elastomeric phase may provide 5 to 95 wt. %, or about 5to about 95 wt. %, of the total graft copolymer, more specifically, 20to 90 wt. %, about 20 to about 90 wt. %, and even more specifically, 40to 85 wt. %, or about 40 to about 85 wt. % of the elastomer-modifiedgraft copolymer, the remainder being the rigid graft phase. Depending onthe amount of elastomer-modified polymer present, a separate matrix orcontinuous phase of ungrafted rigid polymer or copolymer may besimultaneously obtained along with the elastomer-modified graftcopolymer.

Specific encapsulating polymers include polystyrene, copolymers ofpolystyrene, poly(alpha-methylstyrene), poly(alpha-ethylstyrene),poly(alpha-propylstyrene), poly(alpha-butylstyrene),poly(p-methylstyrene), polyacrylonitrile, polymethacrylonitrile,poly(methyl acrylate), poly(ethyl acrylate), poly(propyl acrylate), andpoly(butyl acrylate), poly(methyl methacrylate), poly(ethylmethacrylate), poly(propyl methacrylate), poly(butyl methacrylate);polybutadiene, copolymers of polybutadiene with propylene, poly(vinylacetate), poly(vinyl chloride), poly(vinylidene chloride),poly(vinylidene fluoride), poly(vinyl alcohols), acrylonitrile-butadienecopolymer rubber, acrylonitrile-butadiene-styrene (ABS), poly(C4-8 alkylacrylate) rubbers, styrene-butadiene rubbers (SBR), EPDM rubbers,silicon rubber and combinations comprising at least one of the foregoingencapsulating polymers.

In another embodiment, the encapsulating polymer comprises SAN, ABScopolymers, alpha-(C1-3)alkyl-styrene-acrylonitrile copolymers,alpha-methylstyrene-acrylonitrile (AMSAN) copolymers, SBR, andcombinations comprising at least one of the foregoing. In yet anotherembodiment the encapsulating polymer is SAN or AMSAN.

Suitable amounts amount of encapsulating polymer may be determined byone of ordinary skill in the art without undue experimentation, usingthe guidance provided below. In one embodiment, the encapsulatedfluoropolymer comprises 10 to 90 weight percent (wt. %), or about 10 toabout 90 wt. % fluoropolymer and 90 to 10 wt. %, or about 90 to about 10wt. %, of the encapsulating polymer, based on the total weight of theencapsulated fluoropolymer. Alternatively, the encapsulatedfluoropolymer comprises 20 to 80 wt. %, or about 20 to about 80 wt. %,more specifically, 40 to 60 wt. %, or about 40 to about 60 wt. %fluoropolymer, and 80 to 20 wt. %, or about 80 to about 20 wt. %,specifically, 60 to 40 wt. %, or about 60 to about 40 wt. %encapsulating polymer, based on the total weight of the encapsulatedpolymer.

Some embodiments of the disclosure are polymer compositions that excludefiller.

In other embodiments, the polymer compositions comprise a filler,including the fillers and solid compounding ingredients or agentscommonly used in polymeric compositions. Without being bound by theory,it is believed that the advantageous results obtained herein are due toa synergistic interaction between the filler and fluoropolymer, whichinteraction arises during the mixing process described below.

One useful class of fillers is the particulate fillers, which may be ofany configuration, for example spheres, plates, fibers, acicular,flakes, whiskers, or irregular shapes. Suitable fillers typically havean average longest dimension of 1 nanometer (nm) to 500 micrometers(μm), or 1 nanometer to 500 micrometers, specifically 10 nanometer to100 micrometers, or about 10 nanometers to about 100 micrometers. Theaverage aspect ratio (length:diameter) of some fibrous, acicular, orwhisker-shaped fillers (e.g., glass or wollastonite) may be 1.5 to 1000,or about 1.5 to about 1000, although longer fibers are also within thescope of the disclosure. The mean aspect ratio (mean diameter of acircle of the same area: mean thickness) of plate-like fillers (e.g.,mica, talc, or kaolin) may be greater than 5, or greater than about 5,specifically 10 to 100, or about 10 to about 1000, more specifically 10to 200, or about 10 to about 200. Bimodal, trimodal, or higher mixturesof aspect ratios may also be used.

The fillers may be of natural or synthetic, mineral or non-mineralorigin, provided that the fillers have sufficient thermal resistance tomaintain their solid physical structure at least at the processingtemperature of the composition with which it is combined. Suitablefillers include clays, nanoclays, carbon black, wood flour either withor without oil, various forms of silica (precipitated or hydrated, fumedor pyrogenic, vitreous, fused or colloidal, including common sand),glass, metals, inorganic oxides (such as oxides of the metals in Periods2, 3, 4, 5 and 6 of Groups Ib, IIb, IIIa, IIIb, IVa, IVb (exceptcarbon), Va, VIIa, VIIa and VIII of the Periodic Table), oxides ofmetals (such as aluminum oxide, titanium oxide, zirconium oxide,titanium dioxide, nanoscale titanium oxide, aluminum trihydrate,vanadium oxide, and magnesium oxide), hydroxides of aluminum or ammoniumor magnesium, carbonates of alkali and alkaline earth metals (such ascalcium carbonate, barium carbonate, and magnesium carbonate), antimonytrioxide, calcium silicate, diatomaceous earth, fuller earth,kieselguhr, mica, talc, slate flour, volcanic ash, cotton flock,asbestos, kaolin, alkali and alkaline earth metal sulfates (such assulfates of barium and calcium sulfate), titanium, zeolites,wollastonite, titanium boride, zinc borate, tungsten carbide, ferrites,molybdenum disulfide, asbestos, cristobalite, aluminosilicates includingVermiculite, Bentonite, montmorillonite, Na-montmorillonite,Ca-montmorillonite, hydrated sodium calcium aluminum magnesium silicatehydroxide, pyrophyllite, magnesium aluminum silicates, lithium aluminumsilicates, zirconium silicates, and combinations comprising at least oneof the foregoing fillers. Suitable fibrous fillers include glass fibers,basalt fibers, aramid fibers, carbon fibers, carbon nanofibers, carbonnanotubes, carbon buckyballs, ultra-high molecular weight polyethylenefibers, melamine fibers, polyamide fibers, cellulose fiber, metalfibers, potassium titanate whiskers, and aluminum borate whiskers.

Of these, calcium carbonate, talc, glass fibers, carbon fibers,magnesium carbonate, mica, silicon carbide, kaolin, wollastonite,calcium sulfate, barium sulfate, titanium, silica, carbon black,ammonium hydroxide, magnesium hydroxide, aluminum hydroxide, andcombinations comprising at least one of the foregoing are useful. It hasbeen found that mica, talc, silicon carbide, and combinations comprisingat least one of the foregoing fillers are of specific utility.

Alternatively, or in addition to a particulate filler, the filler may beprovided in the form of monofilament or multifilament fibers and may beused either alone or in combination with other types of fiber, through,for example, co-weaving or core/sheath, side-by-side, orange-type ormatrix and fibril constructions, or by other methods known to oneskilled in the art of fiber manufacture. Suitable co-woven structuresinclude, for example, glass fiber-carbon fiber, carbon fiber-aromaticpolyimide (aramid) fiber, and aromatic polyimide fiberglass fiber or thelike. Fibrous fillers may be supplied in the form of, for example,rovings, woven fibrous reinforcements, such as 0-90 degree fabrics orthe like; non-woven fibrous reinforcements such as continuous strandmat, chopped strand mat, tissues, papers and felts or the like; orthree-dimensional reinforcements such as braids.

Optionally, the fillers may be surface modified, for example treated soas to improve the compatibility of the filler and the polymeric portionsof the compositions, which facilitates de-agglomeration and the uniformdistribution of fillers into the polymers. One suitable surfacemodification is the durable attachment of a coupling agent thatsubsequently bonds to the polymers. Use of suitable coupling agents mayalso improve impact, tensile, flexural, and/or dielectric properties inplastics and elastomers; film integrity, substrate adhesion, weatheringand service life in coatings; and application and tooling properties,substrate adhesion, cohesive strength, and service life in adhesives andsealants. Suitable coupling agents include silanes, titanates,zirconates, zircoaluminates, carboxylated polyolefins, chromates,chlorinated paraffins, organosilicon compounds, and reactivecellulosics. The fillers may also be partially or entirely coated with alayer of metallic material to facilitate conductivity, e.g., gold,copper, silver, and the like.

Optionally the polymer composition may further contain one or moreadditives ordinarily incorporated in resin compositions of this type,preferably with the proviso that the additive(s)s are selected so as tonot significantly adversely affect the desired properties of thethermoplastic composition. Mixtures of additives may be used. Suchadditives may be mixed at a suitable time during the mixing of thecomponents for forming the composition. Exemplary additives includeextenders, lubricants, flow modifiers, fire retardants, pigments, dyes,colorants, UV stabilizers, antioxidants, impact modifiers, plasticizers,optical brighteners, flame proofing agents, anti-static agents, blowingagents, and the like.

Suitable antioxidant additives include, for example, organophosphitessuch as tris(nonyl phenyl)phosphite,tris(2,4-di-t-butylphenyl)phosphite,(2,4,6-tri-tert-butylphenyl)(2-butyl-2-ethyl-1,3-propanediol)phosphite,bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite or the like; alkylated monophenols orpolyphenols; alkylated reaction products of polyphenols with dienes,such astetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane,or the like; butylated reaction products of para-cresol ordicyclopentadiene; alkylated hydroquinones; hydroxylated thiodiphenylethers; alkylidene-bisphenols; benzyl compounds; acylaminophenols;esters of beta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid withmonohydric or polyhydric alcohols; esters ofbeta-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid withmonohydric or polyhydric alcohols; esters of thioalkyl or thioarylcompounds such as distearylthiopropionate, dilaurylthiopropionate,ditridecylthiodipropionate,octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionateor the like; amides ofbeta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid or the like, orcombinations comprising at least one of the foregoing antioxidants.Antioxidants are generally used in amounts of about 0.1 to about 5 partsby weight, based on 100 parts by weight of the polymeric portion of thecomposition (matrix polymer, fluoropolymer, and any impact modifier).

Suitable heat stabilizer additives include, for example,organophosphites such as triphenyl phosphite,tris-(2,6-dimethylphenyl)phosphite, tris-(mixed mono-anddi-nonylphenyl)phosphite or the like; phosphonates such asdimethylbenzene phosphonate or the like, phosphates such as trimethylphosphate, or the like, and combinations comprising at least one of theforegoing heat stabilizers. Heat stabilizers are generally used inamounts of 0.1 to 5 parts by weight, or about 0.1 to about 5 parts byweight, based on 100 parts by weight of the polymeric part of thecomposition.

Light stabilizers and/or ultraviolet light (UV) absorbing additives mayalso be used. Suitable light stabilizer additives include, for example,benzotriazoles such as 2-(2-hydroxy-5-methylphenyl)benzotriazole,2-(2-hydroxy-5-tert-octylphenyl)-benzotriazole and 2-hydroxy-4-n-octoxybenzophenone, or the like, or combinations comprising at least one ofthe foregoing light stabilizers. Light stabilizers are generally used inamounts of 0.5 to 20 parts by weight, or about 0.5 to about 20 parts byweight, based on 100 parts by weight of the polymer portion of thecomposition.

Suitable UV absorbing additives include for example,hydroxybenzophenones; hydroxybenzotriazoles; hydroxybenzotriazines;cyanoacrylates; oxanilides; benzoxazinones;2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol (CYASORB5411); 2-hydroxy-4-n-octyloxybenzophenone (CYASORB 531);244,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl1-5-(octyloxy)-phenol(CYASORB1164); 2,2′-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one) (CYASORBUV-3638);1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacryloyl)oxy]methyl]propane(UVINUL 3030); 2,2′-(1,4-phenylene) bis(4H-3,1-benzoxazin-4-one);1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacryloyl)oxy]methyl]propane;nano-size inorganic materials such as titanium oxide, cerium oxide, andzinc oxide, all with particle size less than about 100 nanometers; orthe like, or combinations comprising at least one of the foregoing UVabsorbers. UV absorbers are generally used in amounts of 0.5 to 20 partsby weight, or about 0.5 to about 20 parts by weight, based on 100 partsby weight of the polymer portion of the composition.

Plasticizers, lubricants, and/or mold release agents additives may alsobe used. There is considerable overlap among these types of materials,which include, for example, phthalic acid esters such asdioctyl-4,5-epoxy-hexahydrophthalate;tris-(octoxycarbonylethyl)isocyanurate; tristearin; di- orpolyfunctional aromatic phosphates such as resorcinol tetraphenyldiphosphate (RDP), the bis(diphenyl) phosphate of hydroquinone and thebis(diphenyl) phosphate of bisphenol-A; poly-alpha-olefins; epoxidizedsoybean oil; silicones, including silicone oils; sodium, calcium ormagnesium salts of fatty acids such as lauric acid, palmitic acid, oleicacid or stearic acid; esters, for example, fatty acid esters such asalkyl stearyl esters, e.g., methyl stearate; stearyl stearate,pentaerythritol tetrastearate, and the like; mixtures of methyl stearateand hydrophilic and hydrophobic nonionic surfactants comprisingpolyethylene glycol polymers, polypropylene glycol polymers, andcopolymers thereof, e.g., methyl stearate and polyethylene-polypropyleneglycol copolymers in a suitable solvent; waxes such as beeswax, montanwax, paraffin wax, EBS wax, or the like. Such materials are generallyused in amounts of 0.1 to 20 parts by weight, or about 0.1 to about 20parts by weight, based on 100 parts by weight of the polymer portion ofthe composition.

The term “antistatic agent” refers to monomeric, oligomeric, orpolymeric materials that can be processed into polymer resins and/orsprayed onto materials or articles to improve conductive properties andoverall physical performance. Examples of monomeric antistatic agentsinclude glycerol monostearate, glycerol distearate, glyceroltristearate, ethoxylated amines, primary, secondary and tertiary amines,ethoxylated alcohols, alkyl sulfates, alkylarylsulfates,alkylphosphates, alkylaminesulfates, alkyl sulfonate salts such assodium stearyl sulfonate, sodium dodecylbenzenesulfonate or the like,quaternary ammonium salts, quaternary ammonium resins, imidazolinederivatives, sorbitan esters, ethanolamides, betaines, or the like, orcombinations comprising at least one of the foregoing monomericantistatic agents.

Exemplary polymeric antistatic agents include certain polyesteramidespolyether-polyamide (polyetheramide) block copolymers,polyetheresteramide block copolymers, polyetheresters, or polyurethanes,each containing polyalkylene glycol moieties polyalkylene oxide unitssuch as polyethylene glycol, polypropylene glycol, polytetramethyleneglycol, and the like. Such polymeric antistatic agents are commerciallyavailable, for example Pelestat 6321 (Sanyo) or Pebax MH1657 (Atofina),Irgastat P18 and P22 (Ciba-Geigy). Other polymeric materials that may beused as antistatic agents are inherently conducting polymers such aspolyaniline (commercially available as PANIPOL®EB from Panipol),polypyrrole and polythiophene (commercially available from Bayer), whichretain some of their intrinsic conductivity after melt processing atelevated temperatures. In one embodiment, carbon fibers, carbonnanofibers, carbon nanotubes, carbon black, or any combination of theforegoing may be used in a polymeric resin containing chemicalantistatic agents to render the composition electrostaticallydissipative. Antistatic agents are generally used in amounts of 0.05 to20 parts by weight, or about 0.05 to about 20 parts by weight, based on100 parts by weight of the polymer portion of the composition.

Colorants such as pigment and/or dye additives may also be present.Suitable pigments include for example, inorganic pigments such as metaloxides and mixed metal oxides such as zinc oxide, titanium dioxides,iron oxides or the like; sulfides such as zinc sulfides, or the like;aluminates; sodium sulfo-silicates sulfates, chromates, or the like;carbon blacks; zinc ferrites; ultramarine blue; Pigment Brown 24;Pigment Red 101; Pigment Yellow 119; organic pigments such as azos,di-azos, quinacridones, perylenes, naphthalene tetracarboxylic acids,flavanthrones, isoindolinones, tetrachloroisoindolinones,anthraquinones, anthanthrones, dioxazines, phthalocyanines, and azolakes; Pigment Blue 60, Pigment Red 122, Pigment Red 149, Pigment Red177, Pigment Red 179, Pigment Red 202, Pigment Violet 29, Pigment Blue15, Pigment Green 7, Pigment Yellow 147 and Pigment Yellow 150, orcombinations comprising at least one of the foregoing pigments. Pigmentsare generally used in amounts of 0.1 to 20 parts by weight, or about 0.1to about 20 parts by weight, based on 100 parts by weight of the polymerportion of the composition.

Suitable dyes are generally organic materials and include, for example,coumarin dyes such as coumarin 460 (blue), coumarin 6 (green), nile redor the like; lanthanide complexes; hydrocarbon and substitutedhydrocarbon dyes; polycyclic aromatic hydrocarbon dyes; scintillationdyes such as oxazole or oxadiazole dyes; aryl- or heteroaryl-substitutedpoly (C2-8) olefin dyes; carbocyanine dyes; indanthrone dyes;phthalocyanine dyes; oxazine dyes; carbostyryl dyes;napthalenetetracarboxylic acid dyes; porphyrin dyes; bis(styryl)biphenyldyes; acridine dyes; anthraquinone dyes; cyanine dyes; methine dyes;arylmethane dyes; azo dyes; indigoid dyes, thioindigoid dyes, diazoniumdyes; nitro dyes; quinone imine dyes; aminoketone dyes; tetrazoliumdyes; thiazole dyes; perylene dyes, perinone dyes;bis-benzoxazolylthiophene (BBOT); triarylmethane dyes; xanthene dyes;thioxanthene dyes; naphthalimide dyes; lactone dyes; fluorophores suchas anti-stokes shift dyes which absorb in the near infrared wavelengthand emit in the visible wavelength, or the like; luminescent dyes suchas 7-amino-4-methylcoumarin;3-(2′-benzothiazolyl)-7-diethylaminocoumarin;2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole;2,5-bis-(4-biphenylyl)-oxazole; 2,2′-dimethyl-p-quaterphenyl;2,2-dimethyl-p-terphenyl; 3,5,3″″,5″″-tetra-t-butyl-p-quinquephenyl;2,5-diphenylfuran; 2,5-diphenyloxazole; 4,4′-diphenylstilbene;4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran;1,1′-diethyl-2,2′-carbocyanine iodide;3,3′-diethyl-4,4′,5,5′-dibenzothiatricarbocyanine iodide;7-dimethylamino-1-methyl-4-methoxy-8-azaquinolone-2;7-dimethylamino-4-methylquinolone-2;2-(4-(4-dimethylaminophenyl)-1,3-butadienyl)-3-ethylbenzothiazoliumperchlorate; 3-diethylamino-7-diethyliminophenoxazonium perchlorate;2-(1-naphthyl)-5-phenyloxazole; 2,2′-p-phenylen-bis(5-phenyloxazole);rhodamine 700; rhodamine 800; pyrene; chrysene; rubrene; coronene, orthe like, or combinations comprising at least one of the foregoing dyes.Dyes are generally used in amounts of 0.01 to 20 parts by weight, orabout 0.01 to about 20 parts by weight, based on 100 parts by weight ofthe polymer portion of the composition.

Where a foam is desired, suitable blowing agents include for example,low boiling halohydrocarbons and those that generate carbon dioxide;blowing agents that are solid at room temperature and when heated totemperatures higher than their decomposition temperature, generate gasessuch as nitrogen, carbon 25 dioxide ammonia gas, such asazodicarbonamide, metal salts of azodicarbonamide, 4,4′oxybis(benzenesulfonylhydrazide), sodium bicarbonate, ammoniumcarbonate, or the like, or combinations comprising at least one of theforegoing blowing agents. Blowing agents are generally used in amountsof 0.01 to 15 parts by weight, or about 0.01 to about 15 parts byweight, based on 100 parts by weight of the polymer portion of thecomposition.

Suitable flame retardant that may be added may be organic compounds thatinclude phosphorus, bromine, and/or chlorine. Non-brominated andnon-chlorinated phosphorus-containing flame retardants may be preferredin certain applications for regulatory reasons, for example organicphosphates and organic compounds containing phosphorus-nitrogen bonds.

One type of exemplary organic phosphate is an aromatic phosphate of theformula (GO)₃P═O, wherein each G is independently an alkyl, cycloalkyl,aryl, alkaryl, or aralkyl group, provided that at least one G is anaromatic group. Two of the G groups may be joined together to provide acyclic group, for example, diphenyl pentaerythritol diphosphate, whichis described by Axelrod in U.S. Pat. No. 4,154,775. Other suitablearomatic phosphates may be, for example, phenyl bis(dodecyl) phosphate,phenyl bis(neopentyl) phosphate, phenyl bis(3,5,5′-trimethylhexyl)phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate,bis(2-ethylhexyl) p-tolyl phosphate, tritolyl phosphate,bis(2-ethylhexyl) phenyl phosphate, tri(nonylphenyl) phosphate,bis(dodecyl) p-tolyl phosphate, dibutyl phenyl phosphate, 2-chloroethyldiphenyl phosphate, p-tolyl bis(2,5,5′-trimethylhexyl) phosphate,2-ethylhexyl diphenyl phosphate, or the like. A specific aromaticphosphate is one in which each G is aromatic, for example, triphenylphosphate, tricresyl phosphate, isopropylated triphenyl phosphate, andthe like.

Neutralizing additives may be for example, melamine,polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, ureaderivatives, hydrazine derivatives, amines, polyamides, andpolyurethanes; alkali metal salts and alkaline earth metal salts ofhigher fatty acids, such as for example, calcium stearate, calciumstearoyl lactate, calcium lactate, zinc stearate, magnesium stearate,sodium ricinoleate, and potassium palmitate; antimony pyrocatecholate,zinc pyrocatecholate, and hydrotalcites and synthetic hydrotalcites.Hydroxy carbonates, magnesium zinc hydroxycarbonates, magnesium aluminumhydroxycarbonates, and aluminum zinc hydroxycarbonates; as well as metaloxides, such as zinc oxide, magnesium oxide and calcium oxide; peroxidescavengers, such as, e.g., (C10-C20) alkyl esters ofbeta-thiodipropionic acid, such as for example the lauryl, stearyl,myristyl or tridecyl esters; mercapto benzimidazole or the zinc salt of2-mercaptobenzimidazole, zinc-dibutyldithiocarbamate,dioctadecyldisulfide, and pentaerythritoltetrakis(.beta.-dodecylmercapto)propionate may also be used. Whenpresent, the neutralizers may be used in amounts of 5 to 50 parts byweight, or about 5 to about 50 parts by weight, more specifically 10 to40 parts by weight, or about 10 to about 40 parts by weight, based on100 parts by weight of the polymer portion of the composition.

In yet another embodiment, the optional additive is a polyamidestabilizer, such as, copper salts in combination with iodides and/orphosphorus compounds and salts of divalent manganese. Examples ofsterically hindered amines include but are not restricted totriisopropanol amine or the reaction product of2,4-dichloro-6-(4-morpholinyl)-1,3,5-triazine with a polymer of1,6-diamine, N,N′-Bis(-2,2,4,6-tetramethyl-4-piperidinyl) hexane.

The components of the composition are mixed under conditions of shearand temperature effective to produce the desired characteristics in themixed composition. Suitable mixing methods for achieving the desiredshear and temperature conditions may be, for example, extrusionkneading, roll kneading, or mixing in a two-roll mill, a Banbury mixer,a single screw or twin-screw extruder, a double blade batch mixer, avertical shaft mixer, a planetary mixer, a Becken blade mixer, adispersion blade mixer, a sigma mixer, in continuous batch mixers of thehydrofoil, turbine blade, or CF impeller blade type, static mixers andthe like devices, which are capable of imparting a controlled degree ofshear. In one embodiment a single screw or a twin-screw extruder isused. The twin-screw extruder may be co-rotating, counter rotating,intermeshing, non-intermeshing, or the like, for example a, planetarygear extruder Readco (York, Pa.) continuous mixer. The mixing may beconducted in a continuous or a batch process. When melt blending orreactive melt blending is used, the mixing is generally conducted at atemperature and for a time effective to produce a molten mixture of asubstantially homogenous composition.

The time, temperature, apparatus, component addition sequence andlocation (along an extruder, e.g.), and other conditions of mixing areaccordingly selected so as to produce a composition having an improvedmodulus compared to compositions not containing both filler andfluoropolymer. Those of ordinary skill in the art will be able to adjustthe degree of shear and temperature, as well as other parameters,without undue additional experimentation using the guidance providedherein.

In one embodiment, the polymer compositions may be prepared bypre-combining the matrix polymer, fluoropolymer, and optional fillerprior to mixing under suitable conditions of temperature and shear,although such pre-combining is not necessary. The pre-combining may becarried out in any conventional mixer (e.g., drum mixer, ribbon mixer,vertical spiral mixer, Muller mixer, sigma mixer, chaotic mixer, staticmixer, and the like). Pre-combining is typically carried out at atemperature below the degradation temperature of the matrix polymer,fluoropolymer, and any encapsulating polymer. Alternatively, a portionof the matrix polymer may be pre-combined with the fluoropolymer (withor without one or more additives) to prepare a masterbatch, and then theremaining matrix polymer may be added and mixed therewith later.

In general, suitable mixing (fibrillation) conditions includetemperatures at or above the glass transition temperature of the matrixpolymer and below the softening temperature of the fluoropolymer. Themixing temperature is also preferably below the degradation temperatureof the matrix polymer. Suitable temperatures may be from 20° C. to 450°C., or from about 20° C. to about 450° C., more specifically, 50° C. to400° C., or from about 50° C. to about 400° C., even more specifically,from 100° C. to 300° C., or from about 100° C. to about 300° C. At thesetemperatures, processing may be conducted for about 2 seconds to about10 hours, specifically about 3 seconds to about six hours.

A modulated differential scanning calorimetry (DSC) method fordetermining extent of fibrillation of the fluoropolymer in the variouscompositions was may be used to monitor the course and degree offibrillation. For example a Q1000 differential scanning calorimeter fromTA Instruments may be used to conduct DSC is conduct on approximately 1to 5 mg of sample, and observations recorded around 320 to 360° C.(modulation range). A peak around 330° C. is observed, and may bedeconvoluted into three different peaks, wherein the different peaktemperatures correspond to different forms of fluoropolymer. A plot wasconstructed using the raw data points from MDSC, and through baselineadjustment a clear magnified peak was observed (after subtraction).Deconvolution was made to fit gauss Ian curves around 326° C. for meltcrystallized PTFE, 330° C. for fibrillated PTFE, and 338° C. for nativePTFE (nodal PTFE). The area under each curve was found to have a strongcorrelation with optimization of properties such as tensile modulus. Inparticular, a Node: Fibril ratio may be calculated based on the areaunder 338° C. peak (node) and 330° peak (fibril).

In one embodiment, the mixed fluoropolymer comprises fibrils having anaverage diameter of 5 nanometers to 2 micrometers, or about 5 nanometersto about 2 micrometers. The fluoropolymer may also have an averagefibril diameter of 30 to 750 nanometers, or from about 30 to about 750nanometers, more specifically, 5 to 500 nanometers, or from about 5 toabout 500 nanometers. (Average diameters may be measured by scanningelectron microscopy (SEM)). The ratio of the node fraction to fibrilfraction (as reflected in the area under the curve in the DSCdeterminations) of the mixed fluoropolymers may be less than 2.5, orless than about 2.5, specifically less than 2, or about 2, and even morespecifically less than 1, or less than about 1.

After mixing, the composition so formed may be made into a particulateform, for example by pelletizing or grinding. For example, the moltenmixture from an extruder may be fed into a die. Some non-limitingexamples of suitable dies include an annular die, coat hanger die,spiral mandrel die, crosshead die, T-die, fishtail die, spider die,single, or double roller die, or profile extrusion die.

The described polymer compositions can be molded into useful articles bya variety of means. For example, the polymer compositions can besubjected to injection molding, extrusion molding, rotation molding,foam molding, calendar molding, blow molding, thermoforming, compaction,melt spinning, pipe extrusion and the like, to form articles.Particularly preferred methods include subjecting the polymercompositions of the description to processes comprising foaming, sheetforming, and pipe extrusion.

Because of their advantageous mechanical characteristics, especiallypreferred are articles that will be exposed to ultraviolet (UV) light,whether natural or artificial, during their lifetimes, and mostparticularly outdoor and indoor articles. Suitable articles areexemplified by but are not limited to aircraft, automotive, truck,military vehicle (including automotive, aircraft, and water-bornevehicles), scooter, and motorcycle exterior and interior components,including panels, quarter panels, rocker panels, trim, fenders, doors,decklids, trunk lids, hoods, bonnets, roofs, bumpers, fascia, grilles,mirror housings, pillar appliqués, cladding, body side moldings, wheelcovers, hubcaps, door handles, spoilers, window frames, headlamp bezels,headlamps, tail lamps, tail lamp housings, tail lamp bezels, licenseplate enclosures, roof racks, and running boards; enclosures, housings,panels, and parts for outdoor vehicles and devices; enclosures forelectrical and telecommunication devices; outdoor furniture; aircraftcomponents; boats and marine equipment, including trim, enclosures, andhousings; outboard motor housings; depth finder housings, personalwater-craft; jet-skis; pools; spas; hot-tubs; steps; step coverings;building and construction applications such as glazing, roofs, windows,floors, decorative window furnishings or treatments; treated glasscovers for pictures, paintings, posters, and like display items; wallpanels, and doors; counter tops; protected graphics; outdoor and indoorsigns; enclosures, housings, panels, and parts for automatic tellermachines (ATM); computer; desk-top computer; portable computer; lap-topcomputer; palm-held computer housings; monitor; printer; keyboards; FAXmachine; copier; telephone; phone bezels; mobile phone; radio sender;radio receiver; enclosures, housings, panels, and parts for lawn andgarden tractors, lawn mowers, and tools, including lawn and gardentools; window and door trim; sports equipment and toys; enclosures,housings, panels, and parts for snowmobiles; recreational vehicle panelsand components; playground equipment; shoe laces; articles made fromplastic-wood combinations; golf course markers; utility pit covers;light fixtures; lighting appliances; network interface device housings;transformer housings; air conditioner housings; cladding or seating forpublic transportation; cladding or seating for trains, subways, orbuses; meter housings; antenna housings; cladding for satellite dishes;coated helmets and personal protective equipment; coated synthetic ornatural textiles; coated painted articles; coated dyed articles; coatedfluorescent articles; coated foam articles; and like applications. Thedisclosure further contemplates additional fabrication operations onsaid articles, such as, but not limited to, molding, in-mold decoration,baking in a paint oven, lamination, and/or thermoforming. The articlesmade from the composition of the present disclosure may be used widelyin automotive industry, home appliances, electrical components, andtelecommunications.

ASPECTS

The present disclosure pertains to and includes at least the followingaspects.

Aspect 1. A polymer composition comprising: a matrix polymer componentcomprising a crystalline or semi-crystalline polymer; and 0.1 wt. % to15 wt. %, based on the weight of the polymer composition, of afibrillated fluoropolymer, a fibrillated fluoropolymer encapsulated byan encapsulating polymer, or a combination thereof.

Aspect 2. A polymer composition comprising: a matrix polymer componentcomprising a crystalline or semi-crystalline polymer; and about 0.1 wt.% to about 15 wt. %, based on the weight of the polymer composition, ofa fibrillated fluoropolymer, a fibrillated fluoropolymer encapsulated byan encapsulating polymer, or a combination thereof.

Aspect 3. The polymer compositions of any of the preceding aspects,wherein the matrix polymer component comprises polybutyleneterephthalate, polyethylene terephthalate, polypropylene, nylon, linearlow-density polyethylene, low-density polyethylene, high densitypolyethylene, polytrimethylene terephthalate, polyethylene naphthalate,polybutylene naphthalate, or a combination thereof.

Aspect 4. A polymer composition consisting of: a matrix polymercomponent comprising a crystalline or semi-crystalline polymer; and 0.1wt. % to 15 wt. %, based on the weight of the polymer composition, of afibrillated fluoropolymer, a fibrillated fluoropolymer encapsulated byan encapsulating polymer, or a combination thereof.

Aspect 5. A polymer composition consisting of: a matrix polymercomponent comprising a crystalline or semi-crystalline polymer; andabout 0.1 wt. % to about 15 wt. %, based on the weight of the polymercomposition, of a fibrillated fluoropolymer, a fibrillated fluoropolymerencapsulated by an encapsulating polymer, or a combination thereof.

Aspect 6. The polymer compositions of any of the preceding aspects,wherein the matrix polymer component consists of polybutyleneterephthalate, polyethylene terephthalate, polypropylene, nylon, linearlow-density polyethylene, low-density polyethylene, high densitypolyethylene, polytrimethylene terephthalate, polyethylene naphthalate,polybutylene naphthalate, or a combination thereof.

Aspect 7. A polymer composition consisting essentially of: a matrixpolymer component comprising a crystalline or semi-crystalline polymer;and 0.1 wt. % to 15 wt. %, based on the weight of the polymercomposition, of a fibrillated fluoropolymer, a fibrillated fluoropolymerencapsulated by an encapsulating polymer, or a combination thereof.

Aspect 8. A polymer composition consisting essentially of: a matrixpolymer component comprising a crystalline or semi-crystalline polymer;and about 0.1 wt. % to about 15 wt. %, based on the weight of thepolymer composition, of a fibrillated fluoropolymer, a fibrillatedfluoropolymer encapsulated by an encapsulating polymer, or a combinationthereof.

Aspect 9. The polymer compositions of any of the preceding aspects,wherein the matrix polymer component consists essentially ofpolybutylene terephthalate, polyethylene terephthalate, polypropylene,nylon, linear low-density polyethylene, low-density polyethylene, highdensity polyethylene, polytrimethylene terephthalate, polyethylenenaphthalate, polybutylene naphthalate, or a combination thereof.

Aspect 10. The polymer compositions of any of the preceding aspects,wherein the matrix polymer component comprises polybutyleneterephthalate, polyethylene terephthalate, or polypropylene.

Aspect 11. The polymer composition of any of the preceding aspects,wherein the fluoropolymer comprises polytetrafluoroethylene,polyhexafluoropropylene, polyvinylidene fluoride,polychlorotrifluoroethylene, ethylene tetrafluoroethylene, fluorinatedethylene-propylene, polyvinyl fluoride, ethylenechlorotrifluoroethylene, or a combination thereof.

Aspect 12. The polymer composition of any of the preceding aspects,wherein the encapsulating polymer comprises a styrene-acrylonitrilecopolymer, an acrylonitrile-butadiene-styrene copolymer,alpha-alkyl-styrene-acrylonitrile copolymer, analpha-methylstyrene-acrylonitrile copolymer, a styrene-butadiene rubber,or a combination thereof

Aspect 13. The polymer composition of any one of the preceding aspects,wherein the fluoropolymer is polytetrafluoroethylene.

Aspect 14. The polymer composition of any one of the preceding aspects,wherein the fluoropolymer encapsulated by an encapsulating polymer isstyrene-acrylonitrile copolymer encapsulated polytetrafluoroethylene.

Aspect 15. The polymer composition of any one of the preceding aspects,wherein the matrix polymer component is polybutylene terephthalate.

Aspect 16. The polymer composition of any one of aspects 1 to 15,wherein the matrix polymer component is polyethylene terephthalate.

Aspect 17. The polymer composition of any one of aspects 1 to 15,wherein the matrix polymer component is polypropylene.

Aspect 18. The polymer composition of aspect 17, wherein thepolypropylene is a random polymer, a co-polymer, or a homopolymer.

Aspect 19. The polymer composition of any one of the preceding aspects,comprising 1 wt. % to 10 wt. %, based on the weight of the polymercomposition, of the fluoropolymer.

Aspect 20. The polymer composition of any one of the preceding aspects,comprising about 1 wt. % to about 10 wt. %, based on the weight of thepolymer composition, of the fluoropolymer.

Aspect 21. The polymer composition of any one of the preceding aspects,having a complex viscosity, measured at a 0.1 rad/sec, of between 4500Pa·s and 70,000 Pa·s, measured at a temperature of between 230° C. and260° C.

Aspect 22. The polymer composition of any one of the preceding aspects,having a complex viscosity, measured at a 0.1 rad/sec, of between about4500 Pa·s and about 70,000 Pa·s, measured at a temperature of betweenabout 230° C. and about 260° C.

Aspect 23. The polymer composition of any one of the preceding aspects,having an extensional viscosity of between 11,000 and 90,000 Pa·s at amaximum henky strain of 2.0 at a strain rate of 1 s⁻¹, measured at atemperature of between 230° C. and 260° C.

Aspect 24. The polymer composition of any one of the preceding aspects,having an extensional viscosity of between about 11,000 and about 90,000Pa·s at a maximum henky strain of 2.0 at a strain rate of 1 s⁻¹,measured at a temperature of between about 230° C. and about 260° C.

Aspect 25. The polymer composition of any one of the preceding aspects,having a tensile modulus of greater than 2450 MPa to 3000 MPa.

Aspect 26. The polymer composition of any one of the preceding aspects,having a tensile modulus of greater than about 2450 MPa to about 3000MPa.

Aspect 27. The polymer composition of any one of the preceding aspects,having a notched impacted strength of greater than 3.5 KJ/m² to 10KJ/m².

Aspect 28. The polymer composition of any one of the preceding aspects,having a notched impacted strength of greater than about 3.5 KJ/m² toabout 10 KJ/m².

Aspect 29. An article comprising the composition of any one of thepreceding aspects.

Aspect 30. The article of aspect 29, produced using a process comprisingfoaming, sheet forming, or pipe extrusion.

Aspect 31. A method comprising: subjecting a polymer composition of anyone of aspects 1 to 22 to a process comprising foaming, sheet forming,or pipe extrusion.

Aspect 32. A method comprising: subjecting a polymer composition of anyone of aspects 1 to 22 to a process consisting of foaming, sheetforming, or pipe extrusion.

Aspect 33. A method comprising: subjecting a polymer composition of anyone of aspects 1 to 22 to a process consisting essentially of foaming,sheet forming, or pipe extrusion.

The following examples are provided to illustrate the compositions,processes, and properties of the present disclosure. The examples aremerely illustrative and are not intended to limit the disclosure to thematerials, conditions, or process parameters set forth therein.

EXAMPLES Materials

PBT 315 (milled PBT) (BASF-GE Schwartzheide)

RAMAPET (milled, regular PET) (Indorama)

TSAN (SAN-encapsulated PTFE). TSAN is a 1:1 ratio of SAN and PTFE.(SABIC)

ALGOFLON DF210 (PTFE) (Solvay Solexis S.P.A.)

108MF10 (PP-copolymer) (SABIC)

670KH (PP-random) (SABIC)

520P (PP-homopolymer) (SABIC)

Example 1

Polypropylene (random, co-polymer, or homo-polymer) was compounded withvarying amounts of TSAN (0.15 wt. % to 10 wt. %) and PTFE (0.15 wt. % to5 wt. %) using a ZSK-25 twin-screw extruder (Krupp Werner andPfleiderer, GmbH, Germany) at a screw speed of 300 rpm. The temperatureof the extruder was set at approx. 50° C. for the feeding section and upto 230° C. in the melting zone by gradually increasing the temperatureaccording to the profile along the length of the extruder:50/70/120/190/220/230/230/230/230/230/230/230° C.

Example 2

Polybutylene terephthalate was compounded with varying amounts of TSAN(0.15 wt. % to 10 wt. %) and PTFE (0.15 wt. % to 5 wt. %) using a ZSK-25twin-screw extruder (Krupp Werner and Pfleiderer, GmbH, Germany) at ascrew speed of 300 rpm. The temperature of the extruder was set atapprox. 40° C. for the feeding section and up to 270° C. in the meltingzone, by gradually increasing the temperature according to the profilealong the length of the extruder:40-70-190-240-270-270-270-270° C.

Example 3

Polyethylene terephthalate was compounded with varying amounts of TSAN(0.15 wt. % to 10 wt. %) and PTFE (0.15 wt. % to 5 wt. %) using a ZSK-25twin-screw extruder (Krupp Werner and Pfleiderer, GmbH, Germany) at ascrew speed of 300 rpm. The temperature of the extruder was set atapprox. 40° C. for the feeding section and up to 280° C. in the meltingzone, by gradually increasing the temperature according to the profilealong the length of the extruder :40-70-190-240-270-270-270-270° C.

Example 4

Pipe extrusion of PBT with 1% PTFE was done at a melt temperature ofabout 266° C., with a screw speed of 21 revolutions per minute (rpm)with a pull speed of 2.8 meters per minute (m/min) and diameter of 19.6millimeters (mm). Pipe extrusion was not possible using PBT withoutPTFE.

Example 5

Foaming was carried out at 200° C. using a chemical blowing agent, e.g.,isobutane, on samples of PBT with PTFE and PBT without PTFE. The PBTwithout PTFE sample had poor surface finish and was found to be brittle.The PBT with 1% PTFE samples showed very good surface finish with goodmechanical properties, e.g., ductility.

Example 6

Complex viscosity [Eta*, η* at frequency in units of radians per second(rad/s)] for embodiments of the disclosure were conducted at 250° C.using ISO 6721-10:1999. See, e.g., FIGS. 1 and 2. As shown in FIG. 1,varying the amount of PTFE present in the PBT samples affects theviscosity. The addition of PTFE to the PBT polymer increased theviscosity of the PBT sample. At 0.1 rad/sec, samples having PTFE (at2.5% and 5%) exhibited a much greater complex viscosity. The 2.5% and 5%PTFE samples exhibited a complex viscosity of greater than 1000 Pa·s,and greater than 4500 Pa·s, while the sample at 0% PTFE exhibited acomplex viscosity of well below 1000 Pa·s throughout the range offrequencies observed, between 0.1 rad/s and 1000 rad/s. A similar trendmay be observed for PET based samples as shown in FIG. 2. The complexviscosity of a PET sample having 1% PTFE also exhibited a complexviscosity greater than 4500 Pa·s at 0.1 rad/s.

Example 7

Extensional viscosity [η* at frequency in units of rad/s] forembodiments of the disclosure was measured using the SER (SentmanatExtension Rheometer) Universal Testing Platform (Xpansion Instrumentsfor use on the ARES-G2). The samples used in this test were 10mm×20mm×0.5 mm. The tests were conducted at 250° C. for PBT samples, at 260°C. for PET samples, and at 230° C. for PP samples, using a constantstrain rate of 1 s⁻¹. The data of extensional viscosity vs. time wasrecorded. See FIGS. 3 through 7. In FIG. 3, PET samples included samplesincluded 0% PTFE, 3% TSAN, 10% TSAN, 2.5% PTFE, and 5% PTFE. Theseexamples demonstrate the formation of PTFE fibrils oriented underextrusion and injection molding and the effect of the PTFE on thepolymer viscosity. The curve corresponding to 0% PTFE exhibited thelowest extensional viscosity values. Increasing amounts of PTFEcorresponded to an increase in the viscosity as can be seen in thecurves for 2.5% and 5% PTFE (the curves adjacent the lowest curvecorresponding to 0% PTFE). A further enhancement of viscosity isobserved in the samples containing TSAN. This may be attributed to PTFEnot being miscible with the molten polymer in-spite of the high polarityof PTFE due to the high crystalline nature of PTFE (>90%). The samplescontaining TSAN at 3% and 10% tend to exhibit greater viscosity,particularly between 0.01 and 1 seconds.

FIG. 4 shows the extensional viscosity for a PET sample at 1% PTFE. Asshown, the viscosity of the polymer improves over time under stress.FIGS. 5, 6, and 7 show the effect of the addition of PTFE and TSAN inpolypropylene polymer samples. In FIG. 5, the curves for a) the randompolypropylene polymer (PP) neat and b) the random PP polymer having 0.5%PTFE, overlap and have the lowest extensional viscosity. Additionalamounts of PTFE (corresponding to curve with 2.5% PTFE) and TSAN (1%)increase the extensional viscosity of the random polypropylene polymer.The random PP polymer exhibiting the greatest extensional viscosity had10% PTFE. Similar trends are apparent in FIGS. 6 and 7 corresponding toPP copolymer and homopolymer, respectively. In FIG. 6, the PP copolymerexhibited the lowest extensional viscosity. The inclusion of 1 wt. %TSAN improved the extensional viscosity (middle curve). At 2.5% PTFE,the PP copolymer exhibited the greatest extensional viscosity. For thePP Homopolymer of FIG. 7, the inclusion of 1% TSAN improved theextensional viscosity to greater than 10000 Pa·s.

Example 8

Tensile modulus for embodiments of the disclosure was measured accordingto ISO 527. See, e.g., FIG. 8. As shown, the tensile modulus increasedwith increasing amounts of PTFE in the PBT polymer.

Example 9

Notched impact strength for embodiments of the disclosure was measuredaccording to ISO 180. See, e.g., FIG. 9. Notched impact strengthincreased with increasing amounts of PTFE in the PBT polymer.

1. A polymer composition comprising: a matrix polymer componentcomprising polypropylene, nylon, linear low-density polyethylene,low-density polyethylene, high density polyethylene, or a combinationthereof; and 0.1 wt. % to 15 wt. %, based on the weight of the polymercomposition, of a fibrillated fluoropolymer, a fibrillated fluoropolymerencapsulated by an encapsulating polymer, or a combination thereof,wherein the composition has a complex viscosity, measured at a 0.1rad/sec, of between 4500 Pa·s and 70,000 Pa·s, measured at a temperatureof between 230° C. and 260° C., and wherein the composition has anextensional viscosity of between 11,000 and 90,000 Pa·s at a maximumHencky strain of 2.0 at a strain rate of 1 s⁻¹, measured at atemperature of between 230° C. and 260° C.
 2. The polymer compositionsof claim 1, wherein the matrix polymer component further comprisespolybutylene terephthalate, polyethylene terephthalate, polytrimethyleneterephthalate, polyethylene naphthalate, polybutylene naphthalate, or acombination thereof.
 3. (canceled)
 4. The polymer composition of claim1, wherein the fluoropolymer comprises polytetrafluoroethylene,polyhexafluoropropylene, polyvinylidene fluoride,polychlorotrifluoroethylene, ethylene tetrafluoroethylene, fluorinatedethylene-propylene, polyvinyl fluoride, ethylenechlorotrifluoroethylene, or a combination thereof.
 5. The polymercomposition of claim 1, wherein the encapsulating polymer comprises astyrene-acrylonitrile copolymer, an acrylonitrile-butadiene-styrenecopolymer, alpha-alkyl-styrene-acrylonitrile copolymer, analpha-methylstyrene-acrylonitrile copolymer, a styrene-butadiene rubber,or a combination thereof.
 6. The polymer composition of claim 1, whereinthe fluoropolymer comprises polytetrafluoroethylene.
 7. The polymercomposition of claim 1, wherein the fluoropolymer encapsulated by anencapsulating polymer comprises styrene-acrylonitrile copolymerencapsulated polytetrafluoroethylene. 8-9. (canceled)
 10. The polymercomposition of claim 1, wherein the matrix polymer component comprisespolypropylene.
 11. The polymer composition of claim 10, wherein thepolypropylene is a random polymer, a co-polymer, or a homopolymer. 12.The polymer composition of claim 1, comprising 1 wt. % to 10 wt. %,based on the weight of the polymer composition, of the fluoropolymer.13-14. (canceled)
 15. The polymer composition of claim 1, having atensile modulus of greater than 2450 MPa to 3000 MPa.
 16. The polymercomposition of claim 1, having a notched impacted strength of greaterthan 3.5 KJ/m² to 10 KJ/m².
 17. An article comprising the composition ofclaim
 1. 18. The article of claim 17, produced using a processcomprising foaming, sheet forming, or pipe extrusion.
 19. A methodcomprising subjecting a polymer composition of claim 1 to a processcomprising foaming, sheet forming, or pipe extrusion.